Novel pyran compounds



United States Patent C F NOVEL PYRAN COMPOUNDS Gustav W. Rapp, Glen Ellyn, 1!].

No Drawing. Application September 11, 1953, Serial No. 379,727

4 Claims. (Cl. 260-343.5)

Dehydroacetic acid forms metal salts typified by the sodium salt having the empirical formula CsH-rNaO4.2I-Ia and the following structural formula:

O Na.H:O

I have now prepared alkali metal salts of novel cupric compounds of dehydroacetic and gluconic acids by reacting an alkali metal salt of dehydroacetic acid (such as the sodium, potassium or lithium salts) with copper gluconate.

The reaction is best carried out by mixing aqueous solutions of the sodium salt of dehydroacetic acid and copper gluconate. Preferably, the reactants are employed in stoichiometrical proportions, although the reaction will proceed even when one reactant is present in excess. Most suitably, the aqueous solutions of the reactants are of 0.1 molar concentration. The metal salts of the novel cupric compound may then be precipitated by diluting the mixed solutions with a water miscible organic solvent such as acetone or methyl or ethyl or isopropyl alcohol.

By way of specific example, 20.8 grams of sodium dehydroacetate (CeH-1NaO4.2H2O) dissolved in 1 liter of water may be mixed with a solution in 1 liter of water of 45.4 grams copper gluconate [Cu(CeHnO7)a]. The

Patented May 7, 1957 resulting mixture may be diluted with 5 liters of acetone or isopropyl alcohol, to precipitate the sodium salt of the novel cupric compound. The corresponding potassium or lithium salts may be prepared by using appropriate amounts of potassium or lithium dehydroacetates in place of sodium dehydroacetate.

.The sodium salts of the novel compound thus prepared contains 14.7% copper. It is soluble in water at pH values above 4 and below 3, being insoluble at values between 3 and 4.

An acidic compound may be prepared from any one of the above disclosed alkali metal salts by dissolving the said salts in water and reducing the pH of the solu tion to a value of less than 3 or 4, say 2.5, and thereafter precipitating the acidic compound by diluting the reaction mixture with acetone or some other water miscible organic liquid, for instance, one of the above mentioned alcohols. It the pH is reduced to .between 3 and 4, the acidic compound is precipitated and may be filtered ofi.

None of the above disclosed novel compounds has a melting point susceptible to accurate determination.

The novel compounds of this invention are excellent deodorants. For instance, one gram of any one of these compounds will practically completely eliminate the odor of one gram of thioglycolic acid dissolved in water.

Many details may be varied without departing from the principles of this invention, and it is therefore not my intention to limit the patent granted on this invention otherwise than necessitated by the scope of the appended claims.

I claim:

1. A reaction product of aqueous solutions of molecular proportions of copper gluconate and an alkali metal dehydroacetate, the said product containing an alkali metal and about 14.7 copper and being soluble in water at pH values above 4 and below 3.

2. A product according to claim 1 in which said alkali metal is sodium.

3. An acidic product prepared by acidifying an aqueous solution of a product according to claim 1 to a pH value of less than 4.

4. A method of preparing a compound according to claim 1 which comprises mixing aqueous solutions of copper gluconate and an alkali metal dehydroacetate, diluting the resulting mixture with a water miscible or ganic liquid to precipitate a compound according to claim 1, and recovering the precipitated compound.

References Cited in the file of this patent Spencer et al.: J. Pharmacol. Exptl. Therap. 99, pp, 57-68 (1950).

Collie et al.: J. C. S. 65 pp. 259- (1894).

Stone: Drug and Cosmetic Ind. 67, pp. 192-3, 266 274r (1950).

Amer. Perfumer and Essential Oil Review, 61, pp. 269, 274 (April 1953). 

1. A REACTION PRODUCT OF AQUEOUS SOLUTIONS OF MOLECULAR PROPORTIONS OF COPPER GLUCONATE AND AN ALKALI METAL DEHYDROACETATE, THE SAID PRODUCT CONTAINING AN ALKALI METAL AND ABOUT 14.7% COPPER AND BEING SOLUBLE IN WATER AT PH VALUES AOBVE 4 AND BELOW
 3. 